- Nickel-Catalyzed Direct Cross-Coupling of Aryl Sulfonium Salt with Aryl Bromide
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The direct cross-couplings of aryl sulfonium salts with aryl halides could be achieved by using nickel as a reaction catalyst. The reactions proceeded efficiently via C-S bond activation in the presence of magnesium turnings and lithium chloride in THF at ambient temperature to afford the corresponding biaryls in moderate to good yields, potentially serving as an attractive alternative to conventional cross-coupling reactions employing preprepared organometallic reagents.
- Ma, Na-Na,Ren, Jing-Ao,Liu, Xiang,Chu, Xue-Qiang,Rao, Weidong,Shen, Zhi-Liang
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supporting information
p. 1953 - 1957
(2022/03/27)
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- Synthesis of Aryl Methyl Sulfides from Arysulfonyl Chlorides with Dimethyl Carbonate as the Solvent and C1 Source
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A new procedure for the synthesis of aryl methyl sulfides from dimethyl carbonate (DMC) and arylsulfonyl chlorides has been achieved. In this strategy, DMC plays a dual role as both, C1 building block and green solvent. Arylsulfonyl chlorides served as the sulfur precursors, and a variety of aryl methyl sulfides were obtained in moderate to excellent yields with good functional group tolerance. Additionally, alkylsulfonyl chloride and dibenzyl carbonate are proven to be suitable substrates as well.
- Miao, Ren-Guan,Qi, Xinxin,Wu, Xiao-Feng
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supporting information
p. 5219 - 5221
(2021/10/19)
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- PROTEIN-MACROMOLECULE CONJUGATES AND METHODS OF USE THEREOF
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The present disclosure provides protein-macromolecule conjugates, releasable linkers, and macromolecules, as defined herein. The disclosed conjugates provide unique properties that are based at least upon the properties of linker and number of linker-Macromolecule moieties. Also provided herein are a method of synthesis and use of conjugates in treating diseases and disorders.
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Paragraph 0384; 0387
(2021/04/10)
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- Copper-Catalyzed Methylthiolation of Aryl Iodides and Bromides with Dimethyl Disulfide in Water
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An efficient route to aryl methyl sulfides through the copper-catalyzed coupling reaction of aryl iodides or bromides with dimethyl disulfide in water is described. Electron-donating and electron-withdrawing functional groups in the substrates were tolerated, and the corresponding products were obtained in moderate to good yields.
- Wang, Ying-Yu,Wu, Xiang-Mei,Yang, Ming-Hua
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supporting information
(2020/07/20)
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- Identification of MsrA homologues for the preparation of (R)-sulfoxides at high substrate concentrations
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Here we report a methionine sulfoxide reductase A (MsrA) homologue with extremely high substrate tolerance and a wide substrate scope for the biocatalytic preparation of enantiopure sulfoxides. This MsrA homologue which was obtained from Pseudomonas alcaliphila (named paMsrA) showed good activity and enantioselectivity towards a series of aryl methyl/ethyl sulfoxides 1a-1k, with electron-withdrawing or electron-donating substituents at the aromatic ring. Chiral sulfoxides in the R configuration were prepared with approximately 50% of yield and up to 99% enantiomeric excess through the asymmetric reductive resolution of racemic sulfoxide catalyzed by the recombinant paMsrA protein. More importantly, kinetic resolution has been successfully accomplished with high enantioselectivity (E > 200) at initial substrate concentrations up to 320 mM (approximately 45 g L-1), which represents a great improvement in the aspect of the substrate concentration for the biocatalytic preparation of chiral sulfoxides.
- Yang, Jiawei,Wen, Yuanmei,Peng, Liaotian,Chan, Yu,Cheng, Xiaoling,Chen, Yongzheng
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p. 3381 - 3388
(2019/04/01)
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- Biocatalytic Preparation of Chiral Sulfoxides through Asymmetric Reductive Resolution by Methionine Sulfoxide Reductase A
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Here we report an environmentally friendly method for the preparation of chiral sulfoxides under high substrate concentration using recombinant methionine sulfoxide reductase A from Pseudomonas monteilii (pmMsrA) as a biocatalyst. Our results show that this enzyme can effectively accomplish the preparation of (R)-sulfoxides with approximately 50 % yield and 94–99 % enantiomeric excess through asymmetric reductive resolution of racemic sulfoxide. With the establishment of the enzyme regeneration system, the initial substrate concentration could be increased 40–100 times compared to our original report. The (R)-sulfoxides were obtained with high enantioselectivity under the substrate concentration up to 200 mm (approximately 32 g L?1), representing a quite high substrate concentration in biocatalytic preparation of chiral sulfoxides. Moreover, this system showed fairly good activity and enantioselectivity towards a series of ortho- and para-substituted phenyl methyl sulfoxides under high substrate concentration.
- Peng, Liaotian,Wen, Yuanmei,Chen, Yu,Yuan, Zhimei,Zhou, Yang,Cheng, Xiaoling,Chen, Yongzheng,Yang, Jiawei
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p. 3284 - 3290
(2018/06/04)
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- Metal-free S-methylation of diaryl disulfides with di-tert-butyl peroxide
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An efficient approach for S-methylation of diaryl disulfides with di-tert-butyl peroxide under metal-free and neutral conditions was established. The present protocol shows good functional group tolerance to afford aryl methyl sulfides in moderate to good
- Wu, Xiangmei,Wang, Yan
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supporting information
p. 1240 - 1243
(2018/03/08)
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- Enantioselective copper catalysed intramolecular C-H insertion reactions of α-diazo-β-keto sulfones, α-diazo-β-keto phosphine oxides and 2-diazo-1,3-diketones; the influence of the carbene substituent
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Enantioselectivities in C-H insertion reactions, employing the copper-bis(oxazoline)-NaBARF catalyst system, leading to cyclopentanones are highest with sulfonyl substituents on the carbene carbon, and furthermore, the impact is enhanced by increased steric demand on the sulfonyl substituent (up to 91%ee). Enantioselective intramolecular C-H insertion reactions of α-diazo-β-keto phosphine oxides and 2-diazo-1,3-diketones are reported for the first time.
- Shiely, Amy E.,Slattery, Catherine N.,Ford, Alan,Eccles, Kevin S.,Lawrence, Simon E.,Maguire, Anita R.
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supporting information
p. 2609 - 2628
(2017/04/01)
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- Kinetic resolution of phenyl methyl sulfoxides by mammalian methionine sulfoxide reductase A
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Chiral sulfoxides are widely used in organic synthesis as chiral auxiliaries. There are numerous strategies for the preparation of enantiomerically pure sulfoxides, based either on the enantioselective oxidation of sulphides or the enantiospecific reduction of sulfoxides. For both cases, bioconversion techniques have been developed and proposed for large-scale synthesis. Methionine sulfoxide reductase enzymes (MsrA and MsrB) catalyse the stereoselective conversion of methionine sulfoxide to methionine. MsrA can also catalyse the reduction of other exogenous sulfoxides, including p-tolyl methyl sulfoxide. However, the stereoselectivity towards this type of substrate is not yet well characterized. The activity and enantioselectivity of MsrA toward several aryl methyl sulfoxides is presented in this paper.
- Achilli, Cesare,Ciana, Annarita,Minetti, Giampaolo
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supporting information
p. 4781 - 4782
(2017/11/29)
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- B(C 6 F 5) 3 -Catalyzed Reduction of Sulfoxides and Sulfones to Sulfides with Hydrosilanes
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B(C 6 F 5) 3 is shown to catalyze the deoxygenation of sulfoxides and sulfones to the corresponding sulfides with Et 3 SiH as the stoichiometric hydride source. While the method is limited in terms of functional group tolerance, it is applicable to the reduction of alkyl/aryl-, aryl/aryl-, and alkyl/alkyl-substituted sulfoxides, including the benzyl/benzyl-substituted derivative. The same protocol converts alkyl/aryl- but not aryl/aryl-substituted sulfones into sulfides.
- Porwal, Digvijay,Oestreich, Martin
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p. 4698 - 4702
(2017/10/05)
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- Metal-Free, DTBP-Mediated Methylthiolation of Arylboronic Acids with Dimethyldisulfide
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An efficient method for the C-S bond formation via the coupling reaction of arylboronic acids with dimethyldisulfide has been developed under the metal-free conditions. This novel protocol provides an attractive route for the synthesis of aryl methyl sulf
- Wu, Xiang-Mei,Lou, Jia-Ming,Yan, Guo-Bing
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supporting information
p. 2269 - 2273
(2016/10/30)
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- Studies on the synthesis, stability and conformation of 2-sulfonyl-oxetane fragments
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2-(Arylsulfonyl)oxetanes have been prepared as new structural motifs of interest for medicinal chemistry. These are designed to fit within fragment space and be suitable for screening in fragment based drug discovery, as well as being suitable for further elaboration or incorporation into drug-like compounds. The oxetane ring is constructed through an efficient C-C bond forming cyclisation which allows the incorporation of a wide range of aryl-sulfonyl groups. Furthermore, biaryl-containing compounds can be accessed through Suzuki-Miyaura coupling from halogenated derivatives. With a number of oxetane containing fragment compounds available, their pH stability was assessed, indicating good half-life values for mono-substituted aryl sulfonyl oxetanes across the pH range (1 to 10). Solubility and metabolic stability data is also reported. Finally, the conformation of the fragments is assessed computationally, providing an indication of possible binding orientations.
- Morgan,Hollingsworth,Bull
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supporting information
p. 5265 - 5272
(2015/05/13)
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- Organocatalytic visible light mediated synthesis of aryl sulfides
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Photo-sensitized synthesis of arylsulfides from arenediazonium salts in the presence of eosin Y has been developed. This protocol exhibits high functional group tolerance and a wide substrate scope and is an attractive alternative to the thermal reaction that involves explosive intermediates.
- Majek, Michal,Von Wangelin, Axel Jacobi
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supporting information
p. 5507 - 5509
(2013/06/27)
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- Synthesis of functionalized aryl fluorides using organolithium reagents in flow microreactors
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Flow on: Flow microreactors enable the generation of aryl lithium compounds and subsequent electrophilic fluorination with NFSI and N-fluorosultam. The reaction can be successfully accomplished to synthesize various aryl fluorides involving an electron-withdrawing, an electron-donating, and a sterically hindered functional group in good yields. Copyright
- Nagaki, Aiichiro,Uesugi, Yuki,Kim, Heejin,Yoshida, Jun-Ichi
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supporting information
p. 705 - 708
(2013/05/08)
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- Copper-mediated methylthiolation of aryl halides with DMSO
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A copper-mediated methylthiolation of aryl halides with the widely available DMSO is described. The procedure tolerates a series of functional groups such as methoxy, nitro, chloro, fluoro, trifluoromethyl, formyl and methoxycarbonyl groups. Thus, it represents a simple and facile methylthiolation procedure.
- Luo, Fang,Pan, Changduo,Li, Liping,Chen, Fan,Cheng, Jiang
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supporting information; experimental part
p. 5304 - 5306
(2011/06/21)
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- Mild and efficient deoxygenation of sulfoxides to sulfides using HFCL 4/KBH4 system
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HfCl4/KBH4 was found to be a facile, efficient, convenient, and chemoselective system for the deoxygenation of dialkyl, diaryl, and aryl alkyl sulfoxides, especially for the reduction of dibenzyl sulfoxide to the corresponding sulfides under mild conditions. In addition, the HfCl 4/KBH4 system could be used in reduction of some other sulfur-bearing substrates to the corresponding sulfides, such as 2,2'-dibenzothiazolyl disulfide, but this reducing system could not reduce sulfolane, diphenyl sulfone, p-toluenesulfonic acid, and p-toluenesulfonyl chloride to their corresponding thiophenols. Copyright
- Zhang, Jianghua,Gao, Xinqin,Zhang, Chengyi,Zhang, Cheng,Luan, Jiming,Zhao, Defeng
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experimental part
p. 1794 - 1801
(2010/07/14)
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- Efficient synthesis of aryl fluorides
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Chemical Equation Presented Creating C-F bonds: A novel electrophilic fluorination of aryl and heteroaryl Crignard reagents has been discovered and was used for the efficient synthesis of various aryl fluoride derivatives (see picture; THF = tetrahydrofuran).
- Anbarasan, Pazhamalai,Neumann, Helfried,Beller, Matthias
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experimental part
p. 2219 - 2222
(2010/06/17)
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- Deoxygenation of sulphoxides on irradiated TiO2 surfaces
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Irradiation of solutions of sulphoxides in organic solvents in the presence of suspended TiO2 results in the deoxygenation giving sulphides in fairly good yields. The mechanism involves the transfer of an electron from the conduction band of the semiconductor to the sulphoxide.
- Somasundaram,Srinivasan
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p. 1523 - 1525
(2007/10/03)
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- Thiophilic addition of organolithiums to trithiocarbonate oxides (sulfines). Synthesis of β-oxoketene dithioacetals, 1,4-dicarbonyl compounds, and allyl sulfoxides
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Reaction of trithiocarbonates with meta-chloroperoxybenzoic acid in CH2Cl2 at 0°C affords the corresponding S-oxides. These sulfines are relatively stable comppounds which can be purified by chromatography. They react readily with organolithiums in THF at -78°C in a thiophilic manner to give carbanions which are stabilized by three sulfur groups. Hydrolysis affords trithioorthoester oxides. The thermal behaviour of these hindered products has been investigated and new rearrangenrent processes have been evidenced. The former carbanions are soft nucleophiles: 1,4-addition of these intermediates to α-enones was achieved selectively to lead to β-oxo ketenedithioacetals, which are easily transformed into 4-oxoalkanethioates. This 'Umpolung' route allows the formal use of the (alkylthio)carbonyl anion. A thiophilic addition was also observed with allylsilanes in the presence of n-Bu4NF furnishing allyl sulfoxides.
- Leriverend, Catherine,Metzner, Patrick,Capperucci, Antonella,Degl'Innocenti, Alessandro
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p. 1323 - 1342
(2007/10/03)
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- The enantioselective oxidation of sulfides to sulfoxides with Acinetobacter sp. NCIMB 9871, Pseudomonas sp. NCIMB 9872, Xanthobacter autotrophicus DSM 431 (NCIMB 10811) and the Black Yeast NV-2
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Whole cell oxidation of aryl alkyl sulfides to sulfoxides with Acinetobacter sp. NCIMB 9871 is only slightly less enantioselective than isolated enzyme transformation with the cyclohexanone monooxygenase (CHMO) from the same species. Pseudomonas sp. NCIMB 9872 oxidises the same substrates with high and mostly opposite enantioselectivity (73-100%ee). CHMO activity was detected in the black yeast NV-2 and Xanthobacter autotrophicus DSM 431 (NCIMB 10811), but contrary to an earlier report this activity could not be detected in cell free extracts of the latter. Both species oxidised methyl phenyl sulfide exclusively to the corresponding (R)-sulfoxide (100% ee).
- Kelly, David R.,Knowles, Christopher J.,Mahdi, Jassem G.,Taylor, Ian N.,Wright, Michael A.
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p. 365 - 368
(2007/10/03)
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- Photoredox reactions of polypyridyl chromium (III) complexes with arylthioacetic acids in acetonitrile and aqueous media
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The reductive quenching reactions of ,Cr(NN)33+ (NN = 2,2'-bipyridyl, 4,4'-dimethyl-2,2'-bipyridyl and 1,10-phenanthroline) with arylthioacetic acids in acetonitrile and arylthioacetate ions in aqueous media have been studied. The substantial difference in k(q) values between the acetonitrile and aqueous media is traced to the difference in the origin of electron for the reduction of Cr(III) complexes i.e., sulphur in acetonitrile and carboxylate ion in aqueous medium.
- Gnanaraj,Rajagopal,Srinivasan
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p. 9447 - 9456
(2007/10/02)
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- Biomimetic catalysis of SN2 reactions through cation-π interactions. The role of polarizability in catalysis
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Cyclophane hosts 1 and 2 have been shown to be effective catalysts for both the alkylation of quinoline structures to produce quinolinium salts and the dealkylation of sulfonium salts to produce sulfides. Thus, reactions that develop positive charge in the transition state and reactions that destroy positive charge are accelerated. The former observation is not surprising, given the well-documented ability of these hosts to bind cations through the cation-π interaction. The catalysis of the dealkylation reactions, however, along with several other observations, suggests that some other factor is involved in the catalysis. It is proposed that the high polarizability of the transition states is well matched to the very polarizable hosts and that this contributes to the catalysis.
- McCurdy, Alison,Jimenez, Leslie,Stauffer, David A.,Dougherty, Dennis A.
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p. 10314 - 10321
(2007/10/02)
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- POTENTIAL ANTIDEPRESSANTS: 4-(THIOARYLOXY)PIPERIDINES
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Nucleophilic substitution reactions of a series of thio-substituted fluoroarenes with 1-methyl-4-piperidinol, 1-benzyl-4-piperidinol, and 1-methyl-4-phenyl-4-piperidinol in the presence sodium hydride in dimethylformamide gave the title compounds V-XI and XIII.The salts of these bases were pharmacologically tested and salts of compounds V, XI, and XIII showed in behavioural tests properties which are indicative of antidepressant activity.
- Sindelar, Karel,Hrubantova, Marta,Svatek, Emil,Matousova, Oluse,Metysova, Jirina,et.al.
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p. 2240 - 2247
(2007/10/02)
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- Carbophilic versus thiophilic attack in the reaction of metallated aromates and heteroaromates with carbon disulfide
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Copper(I) halides catalyse the formation of carbodithioates RCSSLi in the reaction of aryl- or heteroaryl-lithium reagents with carbon disulfide.Subsequent addition of methyl iodide gives the dithioesters RCSSCH3 in highh yields.Appreciable amounts of the methyl sulfides RSCH3 and tars are obtained when the reaction with CS2 is carried out in the absence of copper(I) salts, especially in the case of more basic organoalkali compounds.
- Verkruijsse, H. D.,Brandsma, L.
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